Photosensitive material comprising polyacetylenic amine salts

ABSTRACT

Amine salts of polyacetylenic compounds containing a carboxylate moiety, preferably in conjunction with a group capable of hydrogen bonding, have unusually high radiation sensitivity, and are useful radiation-sensitive components in imaging systems.

United States Patent [1 Bloom et al.

1*Oct. 29, 1974 l l PHOTOSENSITIVE MATERIAL COMPRISING POLYACETYLENICAMINE SALTS [75] Inventors: Melvin S. Bloom, Rochester; Sally S.

Fico, Bergen, both of N.Y.

[73] Assignee: Eastman Kodak Company,

Rochester, N.Y.

[ Notice: The portion of the term of this patent subsequent to July 3,1990, has been disclaimed.

[22] Filed: Dec. 14, 1972 [2i] Appl. No.: 315,249

Related U.S. Application Data [62] Division of Ser. No. 153,059, June14, 1971, Pat. No.

[52] U.S. Cl 96/88, 260/485 R, 260/537 N [51] Int. Cl G03c H00 [58]Field of Search 96/88; 260/485 R, 537 N [56] References Cited UNITEDSTATES PATENTS 3,50l,297 3/1970 Cremeans 96/88 3,501,302 3/1970 Foltz96/88 3,501,303 3/l970 Foltz et al....

3,50l,308 3/1970 Adelman Primary ExaminerRonald H. Smith AssistantExaminerWon H. Louie, Jr.

Attorney, Agent, or FirmJames L. Lewis 5 Claims, No DrawingsPHOTOSENSITIVE MATERIAL COMPRISING POLYACETYLENIC AMINF. SALTS Thisapplication is a division of copending application Ser. No. 153,059,filed June 14, 1971 now US. Pat. No. 3,743,505.

In general, this application relates to photosensitive crystallinepolyacetylenic compositions of matter. More particularly, it relates tocertain crystalline radia tionsensitive polyacetylenic compoundscontaining at least one ammonium carboxylate moiety, and the preparationand use thereof.

Numerous polyacetylenic compositions of matter are reported inliterature along with some observations of them undergoing color changeupon exposure to light and/or ultraviolet radiation. Included amonginvestigators reporting polyyne compositions are: Arthur Seher,Ferdinand Bohlmann and his coauthors; and E. R. H. Jones and M. C.Whiting and their coauthors. The photosensitive polyacetylenic compoundstaught in the art contain a minimum of two acetylenic linkages as aconjugated system (i.e., C C-C C) and, with only a few exceptions,carbon atoms in alpha positions to the acetylenic carbon atoms, i.e.,those carbon atoms directly connecting to the acetylenic carbon atoms,are bonded directly only to carbon and/or hydrogen atoms. Thesephotosensitive polyacetylenic compositions of matter encompass diynes,triynes, tetraynes, higher polyynes and numerous derivatives and relatedcompounds thereof of various chemical classes ranging from hydrocarboncompounds to acids, esters, diols, to still other compounds of otherchemical classifications containing numerous and varied organic radicalsstemming from the conjugated acetylenic carbon atoms.

As is apparent from publications of the aforemen tioned investigators,methods are known to the art for preparation of polyacetyleniccompositions. Methods also are taught in US. Pat. Nos. 2,816,149;2,941,014; 3,065,283; etc. General preparative methods include:oxidative coupling or oxidative dehydrocondensation reactions ofnumerous terminal acetylenic compounds; to prepare as desired,symmetrical and unsymmetrical polyyne compounds dehydrohalogenationreactions to provide compounds containing actylenic bonds; andvariations, modifications and combinations of such two basic reactionsto provide preparative routes for a variety of polyacetyleniccompositions of matter.

In addition, in US. Pat. No. 3,501,297, there is taught and claimed aprocess for photographic formation of a visual positive image throughemployment of crystals of an alkali metal salt of a polyacetylenicdioicacid having a minimum of two acetylenic linkages as a conjugated system.In other related patents, issuing on Mar. 17, 1970, as US. Pat. Nos.3,501,303; 3,501,302; and 3,501,308, respectively, there are taught andclaimed photosensitive image-receptive elements, a process for formationof a visual print-out image, a process for direct photographic formationof a visual printout image, and radiant-energy sensitive compositions ofenhanced photosensitivity and their process of preparation and theiremployment in a photographic process for direct formation of a visualimage.

We have now found that radiation-sensitive polyacetylenic compoundscontaining at least one ammonium carboxylate moiety exhibit highsensitivity. Various polyacetylenic acids and their lower alkylmonoesters are suitable starting points from which the amine salts ofthis invention may be prepared. US. Pat. No. 3,501,297, issued Mar. 17,1970.'discloses a number of such acids, and includes citations ofpatents and journal articles which include exemplary and illustrativeteachings of known methods for the preparation of polyacetylenicpolyoicacids and their lower alkyl monoesters. For example,9,11-eicosadiynedioic acid and 10,12-docosadiynedioic acid are reportedby Black et al., J. Chem. Soc. (1953), 1787, 1790, 1791, as byproductsof coupling reactions; 9,1 1- eicosadiynedioic also is taught by Seherin Fette u. Seiferi, 55 I953), and 10,12-docosadiynedioic acid also istaught by Seher in Fette u. Seifen, 55, (1953) 95, and in Annalen, 589,222.

Exemplary of such acids and esters are 7,9- hexadecadiynedioic 'acid,8,10-octadecadiynedioic acid, 9,1I-eicosadecadiynedioic acid, 10,12-docosadiynedioic acid, 1 l-l3-tetracosadiynedioic acid, I 2, l4-hexacosadiynedioic acid, octacosadiynedioic acid, 14, l6-triacontadiynedioic acid, 15,l7-dotriacontadiynedioic acid,15,17-tetratriacontadiynedioic acid, and 16,18-hexatriacontadiynedioicacid; and each of the monomethyl, monoethyl, and monopropyl estersthereof.

It is an object of our invention to provide novel salt derivatives ofradiation-sensitive polyacetylenic compounds containing at least onecarboxylic moiety. It is a further object of our invention to provideradiationsensitive polyacetylenic compounds containing at least oneammonium carboxylate moiety. It is an additional object of our inventionto provide radiation-sensitive elements containing the carboxylate saltderivatives of our invention, which elements exhibit improved radiationsensitivity.

The amine salt derivatives of this invention are those having thegeneral formula B--(CH ),(C C),,(CH-

n is an integer greater than 1;

x and y are each integers from 0 to 10;

A is selected from ammonium and substituted ammonium groups, i.e.,

is a hydrogen-bonding group selected from the group consisting of CH orsubstituted methyl group,

COO",

COOR,

CONT-1R CONl-INHR, CONHCONHR, RNI-ICOO, and ROOCNI-I; wherein R,R,R Rare the same or different, and may be H,

alkyl of from 1 to 15 carbon atoms, substituted a1- kyl, or aryl.

R may be H or lower alkyl;

R may be an alkyl or substituted alkyl of from 3 to 10 carbon atoms,such as hydroxy, polyhydroxy, amino, substituted amino, alkylthio, ormethoxy substituted alkyl;

R may be alkyl or phenyl, and

'Propylammonium 3 R may be an alkyl or substituted alkyl of from 1 to 8carbon atoms. a phenyl group, or a substituted phenyl.

Preferred amine salts are those in which B is an amide radical,particularly those containing hydroxy, carboxy, or methoxy substitutedalkyl radicals. Exemplary of such moieties are CONHCH CH Cl-1 OH,

CONHCl-l Cl-1 CH COOH, and

CONHCH CH CH OCH Further, preferred amine salts are those which theammonium carboxylate moiety contains an alkyl substitution, e.g.,COONl-F' R, wherein R is an alkyl or substituted alkyl of from 3 to 6carbon atoms.

The preparation and utilization of the compounds may be more readilyunderstood from the illustrative examples which follow. v Monomethylester of 10,12-Docosadiynedioic Acid This compound is prepared by themethod of U.S. Pat. No. 3,501,297.

EXAMPLE 1 The reaction causes the fluid slurry to be converted to athick paste which is stirred with ether, and the mixture then filteredto separate unreacted starting material from the insoluble product (28g.). The hexylammonium compound is recrystallized from 125 ml. ofethanol, chilling in an ice bath to obtain a white solid, mp. 92-94C.

Calcd. for C H N O (546.98 MW): C, 74.6; H,

11.4; N, 5.1 FoundzC, 74.8; H, 11.3; N, 5.4

EXAMPLE 2 [C H NHCO(CH ),,C I CC I C(CH ),,COO]

l 3 a 1l N-propylcarbamoyl )-9,1 1- eicosadiyne- 1 -carboxylate Amixture of 9.4 gr. (0.025 mole, 376.59) of monomethyl ester of10,12-docosadiynedioic acid and 8.9 g. (0.15 mole, 59.1 1 of propylamineis kept for 2 days at room temperature. The pasty slurry is stirred withdiethyl ether and the solid product filtered off. Recrystallization froman ethanol-ether mixture yields the pure amine.

oun C,

EXAMPLE 3 3-Hydroxypropylammonium 20-[ hydroxypropyl )-carbamoyl]-9,1 1-eicosadiynel carboxylate A mixture of 9.4 g. (0.025 mole, 376.59) ofmonomethyl ester of 10,12-docosadiynedioic acid and 1 1.3 g. (0.12 mole,75.1 1) of 3-hydroxypropylamine is briefly warmed, then kept overnightat room temperature. The product is slurried with ether, thenrecrystallized from an ether-ethanol mixture, obtaining a white solid,mp. 913C.

Calcd. for C H N Q: C. 68.0; H,

Found: C. 68.4;

Amine salts of amide-substituted carboxylic acids can be prepareddirectly from polyynes having both carboxylic ester and carboxylic acidfunctions by treatment with the appropriate amine, preferably a primaryaliphatic amine, but also secondary aliphatic amines and those witharomatic groups. Examples 1, 2, and 3 are illustrative of such preferredcompounds.

Acid treatment of the amine salt of the amidesubstituted carboxylic acidyields the amide-substituted carboxylic acid, the amine salt beingdestroyed. This carboxylic acid can in turn be treated with a differentamine to again form an amine salt of an amidesubstituted carboxylicacid. In this compound, however, the amine residue in the amine and inthe amine salt are different.

These reactions are as follows:

Thus, the following amines are suitable reactants for the preparation ofthe amine salts of the invention:

, Nl-I CH CH CH COOH Nl-1 CHOHCH OH Following the process set forth inthe preceding examples, the following amine salts are prepared:

QQQiQQH Li Q- t angCOO ]2 wherein R is selected from the groupconsisting of CH 2 5. 3 1 C4H91 CSHIIQ e m 3 6 a a a a C l-1 COOH, C l-1C(CH OH) CHOHCH N(C H and cnonca on.

Each crystalline polyacetylenic compound for which a specific example ofpreparation already has been sure to as least one form of radiantenergy, particularly ultraviolet radiation, it will undergo a visiblecolor change. A semiquantitive determination and comparison of thephotosensitive response of various prepared crystalline polyacetyleniccompounds of the specific examples can be made as follows: Thepolyacetylenic compound in an organic solvent is flowed onto a whitesurface, such as that of a white filter paper or white filing card, andsolvent evaporated to leave an adhered deposit of the crystallinepolyacetylenic compound. The deposited crystalline polyyne compound thenis exposed to radiant energy in the ultraviolet range, and the densityof the colored photoproduct measured.

Radiant energy, as used herein in regard to the crystallinepolyacetylenic compositions, is intended to include numerous variantforms of radiant energy encompassing not only the ultraviolet andvisible regions (i.e., actinic radiation) and infrared region of theelectromagnetic spectrum, but also electron beam radiation such as isdeveloped by cathode ray guns, also gamma rays, X-rays, beta rays,electrical corona discharge, and other forms of corpuscular and/orwavelike energy generally deemed to be radiant energy. The variousindividual crystalline polyacetylenic compositions disclosed generallyare not responsive to all forms of radiant energy, but selectivelyrespond to at least one or more of the several variant forms of radiantenergy.

In the practice of the invention there is employed a photosensitiveimage-receptive element comprising a carrier means which serves toposition fixedly crystals of the photosensitive crystallinepolyacetylenic composition of matter. The carrier means functions tohold individual crystals in fixed position in relation to other crystalsso that the element, whether unexposed and exposed, can be handled andmoved without displacement or change in positions of crystals withrespect to' each other. Thus, the element can be moved, rotated, turnedover, lifted, and subjected to like physical handling, and, because ofthe carrier means as a component thereof, be of practical utility formany diverse image-recording applications. In contrast, were a carriermeans not included as a component of the imagereceptive element, as ifone were to use a loose mass of layer of photosensitive crystals, thenalmost any slight movement of the exposed element, and even a slight aircurrent, could disturb and displace crystals from their originalposition with a resultant image on the exposed element becomingdistorted and deformed and not a true image. Such an element devoid ofcarrier means would lack any substantial practical utility forimagerecording purposes.

The carrier means can be in any of several diverse embodiments so longas it functions to hold individual crystals substantially in fixedposition in relation to other crystals. Generally and preferably thecarrier means comprise a binder material, such as a natural or syntheticplastic, resin, colloid or gel and the like wherein the crystals of thephotosensitive crystalline polyacetylenic compositions of matter aredispersed therein and held in fixed position thereby. In such instancesthe polyyne composition is mixed as a dope, solution, emulsion,dispersion or the like with the binder material and then processed toprovide solid films, sheets, coatings and the like containing dispersedcrystals of the photosensitive crystalline polyacetylenic composition ofmatter. Thus, one embodiment of the image-receptive element is a solidsheet, film or the like comprising a binder material as a dispersingmedium to position fixedly therein dispersed crystals of thephotosensitive crystalline polyacetylenic composition. Anotherembodiment of the element is a substrate material or body to whichadheres a film, coating, or the like of the binder material having thedispersed crystals therein. Useful substrate materials include papersheet, glass sheet, plastic film, and other conventional and suitablephotographic quality substrate materials. Still an additional embodimentof the element can comprise the substrate material having adheredthereto a binderfree coating of crystals of the photosensitivecrystalline polyacetylenic composition of matter. Other elementembodiments, as desired, can include a coating of a suitable qualityphotographic coating material on one or more surfaces and interfaces ofthe various element embodiments. In addition other element embodimentscan comprise the polyyne crystals and a support means of any of variouscombinations of the several foregoing components and still othercomponents apparent to those in the art, so long as the carrier meansfixedly positions the photosensitive crystalline polyacetyleniccomposition.

Exemplary substrate materials of utility as components for the carriermeans include: vitreous materials, such as glass, glazed ceramics,porcelain, etc.; fibrous materials, such as cardboard fiberboard, paperincluding bond paper, resin and clay-sized papers, wax or othertransparentized paper, paperboard, etc., cloths and fabrics includingthose of silk, cotton, viscose rayon, etc.; metals, such as copper,bronze, aluminum, tin, etc.; natural polymers and colloids such asgelatin, polysaccharides; natural and synthetic waxes includingparaffin, beeswax, camauba wax; synthetic resins and plastics, includingparticularly polyethylene, polypropylene, polymers and copolymers ofvinylidene and vinyl monomers including polyvinyl chloride,polyvinylidene chloride, vinyl chloride/vinyl acetate, vinylacetate/acrylate, vinyl acetate/methacrylate, vinylidenechloride/acrylonitrile, vinylidene chloride, vinyl acetate, vinylidenechloride/methacrylate, polystyrenes, polyvinyl acetals includingpolyvinyl butyral, polyvinyl formal, polyvinyl alcohol, polyamidesincluding polyhexamethylene adipamides, N-methoxymethylpolyhexamethylene adipamide, natural and synthetic rubbers includingbutadiene-acrylonitrile copolymers, 2-chloro-l,3-butadiene polymers,polyacrylate polymers and copolymers including polymethylmethacrylate,polyethylmethacrylate, polyurethanes, polycarbonates, polyethyleneterephthalate, polyethylene terephthalate/isophthalate copolymers andother esters as by condensing terephthalic acid and its derivatives withpropylene glycol, diethylene glycol, tetramethylene glycol orcyclohexane-l,4-dimethanol, cellulose ethers including methyl cellulose,ethyl cellulose and benzyl cellulose, cellulose esters and mixed estersincluding cellulose acetate, cellulose triacetate, cellulose propionate,cellulose nitrate and cellulose diacetate; and even nonthermoplasticmaterials including cellulose phenolic resins, melamine-formaldehyderesins, alkyd resins, thermosetting acrylic resins, epoxy resins, andnumerous other synthetic resins and plastics as will be apparent tothose skilled in the art.

The base or substrate material may be transparent, translucent or opaqueto the particular radiant energy to which the employed photosensitivecrystalline polyacetylene compound is sensitive. It is selected with dueconsideration of the intended usage of the imaged element and of thespecific radiant energy and technique to be employed in the particularimage-recording application. For example, where the imaging techniquerequires transmission of ultraviolet radiant energy through thesubstrate material to expose the polyacetylenic crystals, the substrateshould possess such a transmission characteristic and may be a celluloseacetate butyrate, cellulose acetate, polyvinyl alcohol, polyvinylbutyral or other suitable transparency. The base or substrate materialmay be adhered directly to the binderfree or binder-dispersedphotosensitive crystals, or indirectly adhered, if desired, by a subbinglayer or coating on the substrate material for any of several purposes,e.g., to alter the substrate transmission of the radiant energy, tochange the substrates reflectivity of the radiant energy, to modifyadherence to the substrate material and for other reasons. Similar tothe base or substrate material, such subbing layer is selected with dueregard to the specific radiant energy and technique to be employed inthe particular imagerecording application. Subbing layers for variousphotographic purposes and methods of coating substrate materials withthe same are well known.

Generally and preferably the element, whether comprised ofbinder-dispersed crystals or comprised of substrate material andbinder-free crystals or binderdispersed crystals, is a flat film, sheet,plate or the like so as to present a flat surface upon which radiantenergy may be directed. However, curved-surfaced and other thanflat-surfaced elements, although generally of lesser utility, are notexcluded.

Exemplary binder materials of utility as components for the carriermeans include: natural and synthetic plastics, resins, waxes, colloids,gel and the like including gelatins, desirably photographic-gradegelatin, various polysaccharides including dextran, dextrin,hydrophyllic cellulose ethers and esters, acetylated starches, naturaland synthetic waxes including paraffin, beeswax, polymers of acrylic andmethacrylic esters and amides, hydrolyzed interpolymers of vinyl acetateand unsaturated addition polymerizable compounds such as maleicanhydride, acrylic and methyacrylic esters and styrene, vinyl acetatepolymers and copolymers and their derivatives including completely andpartially hydrolyzed products thereof, polyvinyl acetate, polyvinylalcohol, polyethylene oxide polymers, polyvinylpyrrolidine, polyvinylacetals including polyvinyl acetaldehyde acetal, polyvinyl butyraldehydeacetal, polyvinyl sodium-o-sulfobenzaldehyde acetal, polyvinylformaldehyde acetal, and numerous other known photographic bindermaterials including a substantial number of aforelisted useful plasticand resinous substrate materials which are capable of being placed inthe form of a dope, solution, dispersion, gel, or the like forincorporation therein of the photosensitive polyacetylenic compositionand then capable of processing to a solid form containing dispersedcrystals of the photosensitive crystalline polyacetylenic composition ofmatter. As is well known in the art in the preparation of smooth uniformcontinuous coatings of binder materials, there may be employed therewithsmall amounts of such conventional coating aids as viscosity controllingagents, leveling agents, dispersing agents, and the like. The particularbinder material employed is selected with due regard to the specificradiant energy and technique to be employed in the particularimage-recording application and invariably is a binder materialpermitting substantial transmission of that specific radiant energy tobe employed. Desirably, the binder material is a nonsolvent, orpossesses only limited solvating properties, for the photosensitivepolyyne so that the polyyne is capable of existence in its crystallineform therein.

Well-known sources, lenses, and optical systems, camera arrangements,focusing and projection systems and the like for the various forms ofradiant energy are used in employing the image-receptive element in thevaried imageforming applications, such as specimen photography, patternmaking, reproduction of written, printed, drawn, typed, and like matter,and the recording of line graphical images by an impinging pointed beamof the radiant energy on the element with either or both the element andpointed beam guided or traveling to trace the image. The resultantimages are directly formed print-out images in that they can be seen bythe human eye to be a visibly distinctly different color thanunirradiated crystals of the element.

The photosensitive image-receptive element may be used in image-formingsystems based on transmissionexposure techniques and reflex-exposuretechniques. Thus, stencils of a material substantially nontransmissiveof the radiant energy may be laid onthe imageforming element with thecut-out portion of the stencil allowing the applied radiant energy tostrike the element according to the desired image or images. If desired,the stencil need not contact the element with the radiant energy beingprojected to pass through the cutout portion of the stencil to strikethe element. The element also can be exposed by contact or projectiontechniques through a two-tone image or process transparency, i.e., aprocess negative or positive (i.e., an image-bearing transparencyconsisting of areas transmissive and opaque to the radiant energy suchas of a socalled line of halftone negative or positive-typetransparency) or a continuous tone negative or positive. Likewise anobject, whose image is to be obtained, may be placed between the radiantenergy source and the element and the radiant energy striking theelement will be of an image pattern dependent on the radiant energyabsorption and transmission characteristics of the particular object.Reflex-exposure techniques are applicable. For example, by ultravioletreflecting optic techniques, the ultraviolet sensitive image-receptiveelements may be used to make photocopies of printed or typed copy.Reflex-exposure techniques are particularly useful for making officecopies from materials having messages on both sides of a page, formaking images of specimens and objects, and for reproducing messages andthe like found on materials not having radiant energy transmissiveproperties conducive to transmissionexposure techniques.

Where the image elements are to be retained for lengthy periods, theyare stored, as in an envelope or opaque container, in a manner excludingany stray irradiation of radiant energy of a form photosensitivelyeffecting the element. This may be effectively accomplished byovercoating the imaged element with a layer of material which absorbsradiation to which the element is photosensitive. Thus, an ultravioletabsorbing layer may be coated over the imaged element. Alternatively,the initially imaged elements may be fixed or converted to a more stableimage state. In fixing, the

unexposed photosensitive crystalline polyyne is placed in a formwhere-at it is no longer substantially photosensitive, as by solvatingit in the binder, changing it from crystalline to liquid state, orwashing it out from the element, and the like. In conversion, theinitial irradiation induced color is transformed to another distinctlydifferent color, which is relatively stable as to exposure to theinitial form of radiant energy inducing the image formation.

A particularly convenient manner to effect a color transformation of theinitially induced image is to carefully heat the imaged element to anappropriate elevated temperature, generally between 20C. less than themelting point of the nonirradiated crystalline photosensitive polyyne,where-at the initial radiant- 1 energy induced colortransformer crystalsand crystal portions transform to another distinctly different visiblecolor. Temperatures approximating and higher than the melting point ofthe nonirradiated photosensitive crystalline polyyne will effect a colortransformation of the initial radiant-energy induced colored polyynecrystals, but in so doing, there may be some loss in sharpness of theimage with some blurring and roughing of the image border or periphery.This can be avoided, or at least minimized, if the colored imagedcrystal portions and crystals are firmly held at these temperatures inposition by the binder and if the imaged crystals are so held as toavoid being overcoated or dissolved in melted unexposed polyyne.

Another manner for effecting color transformation of the blue-coloredimage is exposure to a solvent for the unexposed polyyne. An exposurefor about to seconds at an elevated temperature from about 5 to 10C.lower than employable for heat fixing generally is satisfactory.Methanol, ethanol, toluene, diethyl ether, butyl acetate, carbontetrachloride, acetone, 2- butoxyethanol, and like solvents are usefuland water vapor and aqueous solutions, such as aqueous hydrochloric acidwith water soluble polyyne derivatives. Other useful solvents also willbe apparent.

An advantage of the element, having the image thereof in anotherdistinctly different color than the radiation-induced colored image, isthat this other tion, or by applying a solution of a polyyne to a papersurface and allowing the polyyne to crystallize upon the fibers, or bycoating a dispersion of a water immiscible polyyne solution in anaqueous binder and allowing evaporation to form polyyne crystals in thebinder matrix.

EXAMPLE 4 584 mg of hexylammonium 20-(N-hexylcarbamoyl)- 9,1l-eicosadiynel -carboxylate;

is dissolved in 1.5 ml of cyclohexanone. This solution is filtered andadded to a formulation containing 4.0 ml of a 12 percent aqueous gelatinsolution, 0.5 ml. of a 10 percent alcohol-water (:50) solution ofAlkanol XC (a DuPont wetting agent reported to be a sodiumalkylnaphthalene sulfonate) and 4.5 ml of distilled water. This mixtureis dispersed for seconds with a Branson UltraSonic probe (185 WE, /2inch tip) at maximum intensity. The non-crystalline dispersion is thencoated with a 0.004 inch coating blade on a poly (ethyleneterephthalate) film containing a vinylidene chloridepercent)-acrylonitrile (14 percent)- acrylic acid (6 percent) terpolymersubbing layer overcatoed with a cuprous iodide-cellulose nitrateconduc-v tive layer of the type described in Trevoy, U.S. Pat. No.3,245,833. The coating is chill-set and allowed to dry at roomtemperature. Electron micrographic show a crystal size range of fromabout 0.2 to about 4.0 microns with an average particle size in thecoating of about 0.8 microns.

Similar coatings are prepared utilizing the monomethyl ester of10,12-d0cosadiynedioic acid as a control, and the compounds of Examples2 and 3. The dispersion solvent utilized for these materials is asfollows:

monomethyl ester of l0,l2-docosadiynedioic acid- Ethyl acetate Polyyneof Example 2 above Ethyl acetatecyclohexanone (2:1)

Polyyne of Example 3 above chloroform These coatings are tested asdescribed to yield th Control Example I Example 2 Example 3 Thecoatings, "prepared as above, are tested exposing them to a MineraliteUVS- l 2 ultraviolet lamp. Relative speed is calculated according to theformula:

Relative Speed l0 /T, where T time in seconds required to develop adensity of 1.0 under given exposure conditions. The control isarbitrarily assigned a value of to establish a simple basis for directcomparison.

The invention has been described in detail with particular reference topreferred embodiments thereof, but, it will be understood thatvariations and modifications' can be effected within the spirit andscope of the invention.

We claim:

1. In a photographic element comprised of a carrier means fixedlypositioning discrete crystals of a photosensitive crystallinepolyacetylenic compound having a minimum of two acetylenic linkages as aconjugated system, the improvement in which said polyacetylenic compoundis a polyacetylenic amine salt having the formula:

B-(CH ),(C Ii C),,(CH ),,COO A wherein:

n is an integer greater than I;

x and y are each an integer from to A is NRR'R R? wherein R, R, R and Rare H, alkyl of from 1 to carbon atoms, aryl or substituted alkyl havingsubstituents chosen from the group consisting of hydroxy, amino, carboxyand substitu- 1 ents;

B is selected from the group consisting of COO, COOR, CONHR'",

lenic hexylcarbamoyl )-9,l l-eicosadiynel -carboxylate.

lenic propylcarbamoyl)-9,l l-eicosadiynel -carboxylate.

2. The element of claim 1, wherein said polyacetylenic compound is anamine salt of a polyacetylenic alkylamide.

3. The element of claim 1, wherein said polyacetycompound ishexylammonium 20-(N- 4. The element of claim 1, wherein saidpolyacetycompound is propylammonium 20-(N- 5. The element of claim 1,wherein said polyacetylenic compound is 3-hydroxypropylammoniur'n ZO-[N-(3-hydroxypropyl)-carbamoyl]-9,1 l-eicosadiynel carboxylate.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 33 M391Dated October 29. 197

Inventor) Melvin S. Bloom and Sally S. Fico It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 1, line L L, insert before dehydrohalogenation.

Column 2, line #9, insert -B-- before "is".

Column A, line 37 in the formula change "COOHNR R Ru 2 to --cooH R RSigned and sealed this 6th day of May 1975.

(SEAL) Attest: v

C. MARSHALL DANN RUTH C. MASON Commissioner of Patents and TrademarksAttesting Officer

1. IN A PHOTOGRAPHIC ELEMENT COMPRISED OF A CARRIER MEANS FIXEDLYPOSITIONING DISCRETE CRYSTALS OF A PHOTOSENTIVE CRYSTALLINEPOLYACETYLENIC COMPOUND HAVING A MINIMUM OF TOW ACETYLENIC LINKAGES AS ACONJUGATED SYSTEM, THE IMPROVEMENT IN WHICH SAID POLYACETHLENIC COMPOUNDIS A POLYACETYLENIC AMINE SALT HAVING THE FORMULA
 2. The element ofclaim 1, wherein said polyacetylenic compound is an amine salt of apolyacetylenic alkylamide.
 3. The element of claim 1, wherein saidpolyacetylenic compound is hexylammonium20-(N-hexylcarbamoyl)-9,11-eicosadiyne-1-carboxylate.
 4. The element ofclaim 1, wherein said polyacetylenic compound is propylammonium20-(N-propylcarbamoyl)-9,11-eicosadiyne-1-carboxylate.
 5. The element ofclaim 1, wherein said polyacetylenic compound is 3-hydroxypropylammonium20-(N-(3-hydroxypropyl)-carbamoyl)-9, 11-eicosadiyne-1-carboxylate.